Copper-Mediated Radical Fluorine-Atom Transfer to Sulfonyl Radical: A Dramatic 4-Methoxypyridine 1-Oxide Ligand Effect

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(5), P. 3115 - 3127

Published: Feb. 13, 2024

Although the transition metal-catalyzed radical fluorine atom transfer (FAT) strategy has emerged as a powerful tool for construction of C–F bonds, to our knowledge, this approach rarely been applied formation S–F bonds. Here, we report that 4-methoxypyridine 1-oxide can serve an inexpensive and simple yet effective ligand thus promote transformation copper-mediated challengeable FAT sulfonyl radicals, paving way assembly FSO2 group. Based on concept, three Cu(I)-catalyzed protocols involving site-selective intra- intermolecular fluorosulfonylation inert C(sp3)–H bonds 1,2-aminofluorosulfonylation inactivated alkenes have developed, enabling preparation C(sp3)-rich aliphatic fluorides cannot be easily synthesized by known methods. These practical operationally methods result in high functional group tolerance under mild conditions modification bioactive derivatives highly valued molecules. Detailed mechanistic studies indicate unique role facilitating such rare FATs via outer-sphere pathway.

Language: Английский

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Solvation and its influence on the electronic structure and pharmacological activity of 2-fluoro-6-trifluromethyl acetophenone

Journal of Molecular Liquids, Journal Year: 2024, Volume and Issue: unknown, P. 126154 - 126154

Published: Oct. 1, 2024

Language: Английский

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Synthesis of 4-(Bromodifluoromethylseleno) Isocoumarins via Selenolation/Lactonization of 2-Alkynylbenzoates Enabled by a Multi-Component Reagents System

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 25, 2025

p-CF3BnSeCF2Br was developed as a bromodifluoromethylselenonating reagent, which utilized by combining with mCPBA and Tf2O for the synthesis of 4-(bromodifluoromethylseleno) isocoumarins via selenolation/lactonization 2-alkynylbenzoates. The transformation postulated to proceed multicomponent reagents system-enabled sequence involving oxidation into its selenium sulfoxide, activation generated sulfoxide electrophilic p-CF3BnSeOCF2Br salt, 2-alkynylbenzoates reactive species isocoumarins.

Language: Английский

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Asymmetric Construction of a SeCF₃-Substituted Stereocenter by CuH-Catalyzed Hydroboration of 1-SeCF₃-Alkenes

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 20, 2025

A copper hydride (CuH)-catalyzed regio- and enantioselective hydroboration of 1-trifluoromethylseleno (SeCF3)-alkenes with H-Bpin has been developed. The hydrocupration an in situ generated CuH species is followed by a boration reaction to successfully construct SeCF3- Bpin-substituted chiral carbon center. key success the appropriate choice tBu-modified biphosphine ligands, which enables overwhelming high efficiency.

Language: Английский

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Progress in Photocatalyzed Trifluoromethylthiolation and Trifluoromethylselenolation Reactions

Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: May 29, 2024

Abstract The trifluoromethylthio (SCF3) and trifluoromethylselanyl (SeCF3) groups possess high electron-withdrawing ability, excellent lipophilicity, good stability, bioavailability, they are promising structural motifs in drug design development. Photoredox catalysis has clear benefits; it is a mild sustainable methodology for the modification of chemical structures that enables variety reactions unattainable using classical ionic chemistry. This review focuses on light-initiated trifluoromethylthiolation trifluoromethylselenolation with diverse SCF3 SeCF3 reagents. Representative transformations either photocatalysts or through EDA complexes, as well possible reaction mechanisms, all discussed this article. 1 Introduction 2 Photocatalyzed Trifluoromethylthiolation 2.1 MSCF3 (M = H, [Me4N], Ag) 2.2 XSCF3 (X Cl, CF3S) 2.3 ArSO2SCF3 2.4 N–SCF3 Reagents 2.5 Other 3 Trifluoromethylselenolation 3.1 [Me4N][SeCF3] 3.2 ArSO2SeCF3 4 Summary

Language: Английский

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Synthesis of Trifluoromethylselenolated Spiro[5.5]trienones/Spiro[4.5]trienones via Electrophilic Trifluoromethylselenolation Cyclization and Dearomatization

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 15, 2024

Abstract An expedient strategy for the construction of trifluoromethylselenolated spiro[5.5]trienones/spiro[4.5]trienones through a cascade electrophilic trifluoromethylselenolation cyclization and dearomatization has been developed. This sequential process was induced by N ‐trifluoromethylselenophthalimide (Phth‐SeCF 3 ), which an efficient reagent. approach feature mild conditions, broad substrate scope, high functional group tolerance.

Language: Английский

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Copper‐Mediated Decarboxylative Trifluoromethylselenolation of Alkynyl Carboxylic Acids with [Me₄N][SeCF₃]

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 30, 2024

Abstract The synthesis of alkynyl trifluoromethyl selenoethers from copper‐mediated aerobic decarboxylative trifluoromethylselenolation carboxylic acids with [Me 4 N][SeCF 3 ] is reported. reaction proceeded smoothly under mild conditions and enabled the facile conversion both aryl alkyl to corresponding in good yields, demonstrating that nucleophilic reagent feasible at ambient temperature without irradiation. Advantages method include use bench‐stable non‐volatile as starting materials, readily accessible SeCF reagent, excellent functional group tolerance, avoidance harsh conditions. This represents first a source.

Language: Английский

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